Water-soluble reactive dyes of the phthalocyanine series



United States Patent This invention relates to water-soluble reactive dyes of the phthalocyanine series which have the formula wherein PC represents a phthalocyanine radical,

A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical,

A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical,

A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical,

R represents the radical of an azo dye, I

R represents a substituted or unsubstituted divalent'aliphatic, aromatic, cycloaliphatic or araliphatic radical or together with A A and the two Ns a divalent heterocyclic radical,

W represents an amino group which may be monoor di-substituted, and

Z represents ,a reactive substituent, i.e. a radical capable of forming a chemical linkage with the substrate,

and wherein m, n, p and q each has a value of at least 1 but not more than 3 and the sum of ml+n+p+q is at least 4 but not more than 6 and wherein the dye of Formula I contains the number of water-solubilizing groups necessary for water-solubility.

A series of especially interesting dyes of the Formula I comprises those in which PC representsv a copperphthalocyanine radical, A A and A each represents a hydrogen atom or one of.A A and A represents an optionally substituted, eg by 'OH, alkyl radical with 1 to 5 carbon atoms and the two others represent hydrogen atoms, R represents the radical of a water-soluble monoazo dye of the benzene-azo-benzene or of the benzene-azo-S-pyrazolone series, R representsthe 1,3- or 1,4-phenylene radical which may bear a sultonic acid grouper a 1,2-ethylene, 1,2- or 1,3-propylene radical, Z represents a halogenoalkanoyl or halogenoalkenoyl radical with 2 to 3 carbon atoms, a 2,4-dich1oro-1,3,5-triazinyl-6-radical, a 2-amino or 2 -substituted amino-4- chloro-1,3,5-triazinyl-2-radical, the substituent being alkyl or hydroxyalkyl with 1 to 3 carbon atoms or monoor disulfophenyl, a 2,6- or -4.6-dichloro or 2,5,6-:or 4,5,6- trichloropyrimidyl radical or a 2,4-dichloro 6-hydrogenor -6-methylpyrimidyl-S-methylene radical, W represents an amino group and the sum of m, n, p and q is 5 or 6 and the whole molecule contains 4 to 6 sulfonic acid groups which may be partially replaced by sulfonic acid amide or carboxylic acid groups.

The process for the production of these dyes comprises 3,133,050 Patented May 12, 1 964 X represents hydrogen, a substituted or unsubstituted acyl radical or a reactive substituent, and, according to the final dye desired, with water and/or ammonia and/or a primary or secondary amine and condensing the reaction products without further processing when X stands for hydrogen, or after cleavage of the acyl radical when X stands for this radical, with at least 1 mole of a compound which is condensible with a primary or secondary amino group and is capable of forming a chemical linkage with the substrate, the starting products being so chosen that the final dye contains the number of watersolubilizing groups necessary for water-solubility.

Examples of suitable water-solubilizing groups are the sulfonic acid, carboxylic acid, methylsulfonyl, ethylsulfonyl and sulfonamide groups, of which the lastnamed may be monosubstituted preferably by low-molecular (i.e. with 1 to 5 carbon atoms) hydrocarbon radicals. It is advantageous for the dyes of Formula I to contain at least two sulionic acid groups in order to possess the water-solubility necessary for use iri practice, but it is hardly possible to introduce more than eight sulfonic acid groups into the dye molecule.

Therefore the dyes of Formula I contain preferably four to six sultonic acid groups which may in part be replaced by carboxylic acid, alkylsulfonyl or sulfonamide groups, which latter may be monosubstituted. It is to be noted that the water-solubilizing eiTect of the carboxylic acid group and the unsubstituted or monosubstituted sulfonarm'de group is dependent on the pH value. At room temperature only the alkali metal salts of these groups show really good effectiveness, the acid forms being much less elfective. v

Other weakly to very weakly water-solubilizing groups such as hydroxyl, acetylamino, carbomethoxyarnino, carbethoxyamino anddisubstituted sulfonamide groups are of only secondary importance.

The chlorides of phthalocyanine-di-, -trior -tetrasulfonic acids and their mixtures which aroused as starting products are derived from metal-free phthalocyanine or from metal-containing phthalocyanine, e.g. cobalt, nickel or preferably copper phthalocyanine. They bear the sultonic acid chloride groups in the positions 3 of the benzene nuclei when they are produced by direct sulfochlorination or in the position 4 when they are produced from the corresponding sulfonic acids.

The aminoazo dyes upon which the radical R is based are preferably water-soluble monoor dis-azo dyes, e.g. 4-amino-1,1'-azobenZene-2', -3- or -4-mono-sulfonic acid or -2,4'- or -2',5'-disulfonic acid, 4-amino-4'-methyl-, -4'- fonic acid, 2-(4'-amino-phenylazo) naphthalene 3,6-,

-4,8-, -S,7- or -6.8-disulfonic acid or -3,6,8- or -4,6,8-trisulfonic acid, 4-amino-2,2-dimethyl-1,1'-azobenzene-4- sulfonic acid, l-(4'-aminonaphthyl-1'-azo)-benzene-2,4- or -2,5- or -4,6- or -4,7'-disu1fonic acid, 1-phenyl-3- methyl-4-(3"- or 4-aminophenyla zo)-5-pyrazolone-2-,

acid, 1-hydroXy-2-(3'- or 4-aminophenylazo)-6- or 7- acylaminonaphthalenea,6'-disulfonic acid, 1-hydroxy-2- (3 or 4'-amino-phenylazo) -8-acylamino-naphthalene-3,5- or -3,6-disulfonic acid, or -3,5,6'- or -3,6,6 -trisulfonic acid, the acyl group being e.g. acetyl, propionyl, benzoyl, carbethoxy or carbomethoxy. Arninoazo compounds insoluble in water or moderately to poorly soluble in water can also be used, e.g. 4-amino-l,l-azobenzene, 4-amino 4-methyl-, -4'-methoxy-, -4'-ethoxyor -4'-chloro-l,1- azobenzene, 4-amino-l,l-azobenzene-3'- or -4'-sulfonic acid amide, 4-amino-1,lGazobenzene-Z or -4'-carboxylic acid, -l-(3'- or 4'-aminophenyl)-3-methyl-4-phenylazo-5- pyrazolone, l-(3 or 4'-aminophenyl)-3-methyl-4-phenyl azo-5-pyrazolone-2"- or -4"-carboxylic acid-3"- or -4"- sulfonic acid amide, l-(3'- or 4'-aminophenyl-3-carboxy- 4-phenylazo-5-pyrazolone, 3-keto-2-(3- or4'-aminophenylazo),-butyric acid phenylamide-2- or -4"-carboxylic acid or -3"- or -4-sulfonic acid amide. The sulfonic acid amide group can of course be replaced by its monoor disubstituted derivatives. When the aminoazo compound used is insoluble, moderately soluble or poorly soluble in water, it is necessary to ensure that the radical of the dye molecule contains the number of watersolu-- bilizing groups necessary for water-solubility. The radical R is preferably an aliphatic radical e.g. an alkylene radical, such as CH -CH CH CH CH I 'CHn(!3H CH CH CH CH or an aromatic radical e.g. a

phenylene radical which may be substituted such as or a cycloaliphatic radical, e.g. a cyclo-hexylene radical such as CHn-CHg CHr-CH:

' -CH 011-, -c on:

CHa-'Cg etc.

' The substituents A A and A represent preferably hydrogen atoms or low-molecular (i.e. containing 1 to about 5 carbon atoms) alkyl, e.g. methyl, ethyl, hydroxyalkyl, e.g. Z-hydroxyethyl, 2- or 3-hydroxypropyl, al-' koxyalkyl, e.g. 2-ethoxyethyl, S-methoxypropyl, 3- or 4 methoXy-butyl, halogcnoalkyl, e.g. 2-chloroethyl, or benzyl radicals. When the radical R is aromatic or cycloaliphatic, it is advisable to choose hydrogen atoms or aliphatic radicals as A and/ or A But if the radical R is aliphatic, A and A may be hydrogen atoms or aliphatic or araliphatic radicals such as aromatic or cycloaliphatic radicals.

The radical W is preferably the amino group, a low molecular monoor dialkylamino group, e.g. methylamino, dimethylamino, ethylamino, diethylamino, a low molecular monoor di-(hydrbxyalkyD-amino group, e.g. Z-hydroxyethylamino, di-(2-hydroxyethyl)-amino, 2- or 3-hydroxypropylamino, 3-hydroxybutylamino, a low molecular'alkoxyalkylamino group e.g. Z-ethoxyethylamino, 3-methoxypropylamino, 3- or 4-methoxybutylamino, a low molecular carboxyor sulfoalkylamino group and its N- methyl and N-ethyl-derivatives, carboxymethylamino, 2-

carboxyethylamino, N-methyl-N-carboxyrnethylamino, 2-

sulfoethylamino, N-methyl-N-Z-sulfoethylamino, N-ethyl- N-2-sulfoethylarnino, a monoor dinuclear arylamino group which may contain 1 to 2 carboxy or 1 to 3 sulfonic acid groups, e.g. phenylamino, 2 or 4-methylphenylamino, 3- or 4-chlorophenylamino, 4-acetylaminophenylamino, 2- or 4-carboxyphenylamino, 2,4- or 2,5-dicarboxyphenylamino, 3- or 4-sulfophenylamino, 2,4- or 2,5- disulfophenylamino, 4,8- or 5,7- or 6,8-disulfonaphthyl-2- amino, 4,6,S-trisulfonaphthyl-2-amin0.

For the reactive component upon which the reactive group Z is based choice is made of compounds which are condensible with a primary or secondary amino group and also are capable of forming a chemical linkage with the substrate, i.e. those which contain a readily cleavable substituent and/ or an unsaturated radical whose multiple linkage is easily capable of addition. Examples of suitable components are functional derivatives of low molecular halogeno alkanoic acids such as chloroacetic acid,

bromoacetic acid, fi-chloroand fi-bromo-propionic acid,

lecular alkanoic acids such as acrylic acid, methacrylic acid; low molecular halogenoalkenoic acids such as a-chloroand a-bromoacrylic acid, ,3- and 'y -chloroor bromo-crotonic acid, 0;,5- and 5,;6-dichloroor dibromoacrylic acid, and the following heterocyclic compounds: tetrameric chloroor bromo-cyan, cyanuric chloride, cyanuric bromide, primary condensation products of a cyanuric halide of the formula ester, alkenyl, e.g. ail-lyl, chlorovinyl, substituted alkyl, e.g.

carboxymethyl, ohloroor tbromome-thyl; 2,4,5,6 tetrachloroor -tetrabromopyrimidine, 5 bromo- 2,4,6 trichloropyrimidine, 2,6 dichloro or -dibromopyrimidine- 4 carboxylic acid ethy-lor -methyl ester, 2,4,5 trichloropyrimidine, 2,4,5 tribromopyrirnidine, 2,6 dichloroor -dibromopyrimidine, 2,4 dichloro 5 chloromethyl 6 methylpyrimididne,'2,4 dibrom-o 5 bromo-' methyl 6 methylpyrimidine, 2,4 dichloro 5 chlorornethylpyrimidine, 2,4 dibromo 5 bromomethylpyrhmar-11, 2,5,6 triohloro 4 methylpyrimidine, 2,5,6 tribromo 4 methylpyrimidine and 2,6 dichloro 4 trichloro-methylpyrimidine.

Examples of suitable diamines containing at least one aromatica-lly bound amino group are: diaminonaphthalenes such as 1,5 diaminonaphthalene, 1,4 diamino 2- rnethylnaphthalene, 1,4 diaminonaphthalene 6 sulfonic acid; diaminodiphenyls such as 4,4 diamine 1,1 diphenyl, 4,4 diamine 2,2 dimethylor -2,2' d1- methoxyor -2,2'-dichloro-1,1-diphenyl or -1,1diphenyl- S-sulfonic acid, 4,4-diamino-1,1-diphenyl-2,2'-disulfonic acid, 4,4 diamino diphenylmethane, 4,4 d-iaminostilbene 2,2 disultonic acid, 1 aminomethyl 3- or -4 aminobenzene and preferably diaminobenzenes such as 1,3- or 1,4 diaminobenzene, 1,3- or 1,4 diamino 6- methyl-, -6 met-hoxyor -6 chlorobenzene, 1,3- or 1,4- diaminobenzene 6 sulfonic acid or -6 carboxylic acid; 1 amino 3- or -4 methylaminobenzene, 1 amino 3- or -4 methylaminobenzene 6 sulfonic acid.

The following may be enumerated as examples of suitable amines of Formula II: N acetylethylene diamine, N acetyl 1,2- or -1,3 propylenediarnine, N acetyl- 1,2- or -2,3- or -1,3- or -1,4 butylenedi-amine, N-acetyl- N methylor N ethylor -N B hydroxyethylethylenedia-mine, N acetyl N methylethylenediamine, N -acety1 N methyl 1,2- or -1,3 propylenediamine, 1 acetylamino 3- or -4 aminobenzene, 1 acetylamino- 3- or -4 methylaminoor -ethyla-minoor -B hydroxyethylaminobenzene, 1 acetylamino 3- or -4 aminoor -methylarnino 6 methylor -6 methoxyor -6 chlorobenzene, 1 aminoor 1 methylarnino 3- or -4 acetylamino 6 methylor -6 methoxyor 6 chlorobenzene, 1 acetylarnine 3-or -4 aminobenze-ne 6 sulfonic acid or -6 carboxylic acid, 1 acetyl-arnino 3- or -4 methylaminoor -ethylamineor -,8 hydroxyethylaminobenzene- -6 sulfonic acid or -6 carboxylic acid, 1 methyl- N acetylamino 3- or -4 -aminobenzene, l N methyl- N acetylamino 3- or -4 methylaminobenzene, l-acetylamino 3- or -4 aminomethylbenzene, 1 acetylamino methyl 3- or -4 aminobenzene, 4-acetylamino 4'- amino 1,1 diphenyl, 4 acetylarnino 4 amino 2,2- dimethylor -2,2' dimethoxyor -2,2' .dichloro 1,1- diphenyl, 4 acetyl'amino 4' amino 1,1 diphenyl- 2,2 disulfonic acid,4 acetyl-amino 4' aminodiphenylmethane, 1 amino 3- or -4 nitrobenzene, 1 amino- 4 methyl 3 nitrobenzene. In the above-mentioned compounds of Formula II the acetyl radical may be replaced by another acyl radical such as pr-opionyl, butyryl, benzoyl, ox-alyl, carbomethoxy or carbethoxy.

.The reaction of the chlorides of a phthalocyanine-di-, -trior -tetra-sulfonic acid with the aminoazo dye and the diamine of Formula II according to the first mode of operation of the process is carried out in organic solution or suspension, e.-g. in an inert organic solvent, in aqueousorganic or preferably in aqueous solution or suspension. It is advisable to work at low temperature, e.g. at to 10 C., or at room temperature or at a higher temperature, in a weakly acid, neutral or weakly alkaline medium, e.g. in the pH region 6 to 9, in the presence of acid-binding agents.

Any sulfonic acid chloride groups which may be present after the condensation reaction with the aminoazo dye and the diamine of Formula II are saponified to sulfonic acid groups or reacted with ammonia or a primary or secondary amine. When the substituent X of the diamine is an acyl group, this group is split ofi,,e.g. by heating with a dilute mineral acid, preferably 410% hydrochloric or sulfuric acid, at 70-100" C. i

As a rule the simplest way of introducing the acid radicals is to use the corresponding acid halides, or in some instances the acid anhydrides. It is :best to work at low temperatures, e.g. 0-20 0., and in the presence of an acid-binding agent such as sodium carbonate, sodium hydroxide, calcium hydroxide or sodium acetate at a weakly acid, neutral or weakly alkaline reaction, eg in the pH region 4 to 9. For acylation, the carboxylic acid chlorides are employed as, such or in solution in two to five times their amount of benzene, chlorobenzene, methyl- Theintroduotion of a dihalogenocyanuric radical is,

best accomplished in aqueous medium at about 0 C. and at a weakly acid reaction, e.g.'at pH values between 3 and 5. The cyanuric halide can be used as such insolid form or in solution in an organic solvent, e.-g. acetone. For the primary condensation products of a cyanuric halide of the Formula IV it is best to choose a temperature of 30-60" C. and a pH value of 4-6, while for the di-, trior tetra-halogenopyrimidines temperatures of 40-to C. are the most suitable. If temperatures higher than about 50 C. are necessary it is advisable to work in vessels equipped with reflux condensers in view of the volatiliity in water vapor of certain halogenopyrimidines. The reaction can be conducted in a weaklyacid, neutral to weakly alkaline medium, preferably in the pH region of 3 to 9. To maintain a constant pH value an acid-binding agent, eg sodium acetate or a phosphate butter, is added to the mixture at the start of the reaction, or small portions of sodium or potassium carbonate or bicarbonate in solid, pulverized form or as an aqueous solution are added during the reaction. Aqueous solutions of sodium or potassium hydroxide are also suitable as neutralizing agents. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction. p

The reaction with the halogenated heterocyclic compounds is so conducted that only one halogen atom reacts with one'exchangeable hydrogen atom of the amino group. For this purpose about one mole of the halogenated heterocyclic compound is employed for each amino group. The phthalocyanine dyeslobtained, which contain at least one reactive group, are precipitated from their aqueous solutions by the addition of salt, filtered off, Washed if necessary and dried. I

The condensation -of the phthalocyanine-di-, -trior e.g. O 10" C., orat room temperature or at a higher temperature, in a weakly acid, neutral or. weakly alkaline medium, eg in the pH region 6-9, in the presence of an acid-binding agent. When the vunreacted diamine contains one aliphatic and one aromatic amino group, the

latter is protected from reacting, eg. by acylation, so that only the aliphatic amino group reacts. with a sulfonic acid chloride group. The aromatic amino .group is of course freed again after the reaction.

Any sulfonic acid chloride groups that are present after the condensation reaction with the. amine of Formula H and the diamine containing at least one aromatically bound amino group are saponified to sulfonic acid groups or reacted with ammonia or a primary or secondary amine. t

The reaction product is precipitated with salt or acid, filtered oif with suction, washed if necessary and dried. The moistpaste or the dried product is dissolved or suspended in water and directly. or indirectly diazotized at low temperature, e.g. -5 to -|-20 C., or preferably at 0 to +5 C. The reaction product can be diazotized immediately after condensation without isolation. But it must be remembered that isolation is at the same time a very effective means of purification and that in the condensation undesirable by-products can be formed and/ or unreacted starting products left after the reaction, so that isolation is to be recommended as the safest procedure.

Depending on the coupling components the coupling reaction iscarriedout 'in an acid, neutral or alkaline medium' at temperatures of 'e.g..5 to 4010. Amines to neutral medium, e.g. inthe pH region of -1.0 to 7.0, Land at temperatures below about 40 (3., eg at to 30 0..

They are dissolved in water, in a dilute acid solution or in afmixture of water orof a dilute acid solution and an organic solvent, e.g. alcohol, acetone, dioxane, di-' methylformamide etc. or finely dispersed, if necessary with the aid of a dispersing'or emulsifying agent. It is convenient to begin the coupling reaction in a distinctly acid medium and to gradually neutralize the acid by the addition of sodium or potassium acetate, carbonate or bicarbonate. With the coupling components containing a phenolic or euolic hydroxyl group it is advisable to work in a1weakly acid, neutral to alkaline medium, e.g. inthe pH region of 3 to 12, at low temperature, e.g.;- 5 to 25 C., or preferably 0 to 15 C.

When the substituent X in Formula ll represents a reactive group, the product is the final dye and-it can be isolated in the usual way. 7 When X stands for an acylamino groupfthis group. is hydrolyzed, e.g. by heating with a dilute mineral acid, preferably 410% hydrochloric or sulfuric acid, at 70100 C. WhenY represents a nitro group, this group is reduced, e.g. by-lheating with sodium sulfide or sodium hydrogen sulfide solution in the alkaline pH region at temperatures of 40 to 60 C., or preferably at 40-50 C.

The new reactive dyes of the phthalocyanine series Owing to' their only moderate substantivity, the unfixed portion of dye iseasy to wash'ofi? from dyeing and prints on cellulosic fibers.

The reactive dyesof the invention which contain two benzene-l-sulfonate.

' Thedyeing, padding and printing or-fixation of the dyes on cellulosic fibers is carried out to best "advantage in alkaline medium, e.g. in the presence of sodium carbonate or bicarbonate, sodium hydroxidesolution, potassium hydroxide solution, sodium m'etasilicate, sodium borate, trisodium phosphate, ammonia, etc. To preclude reduction efiects it is often of advantage to use a mild oxidizing agent in dyeing, padding or printing, e.g. sodium 3-nitrow The addition of fcertain 'quaterni zable amines such as or three water-solubilizing groups, preferably sulfonic acid groups, are well suitable for the exhaustion dyeing of cellulosic fibers and for the acid dyeing of wool, silk and synthetic .polyamide fibers.

The new reactive dyes are suitable for dyeing leather, for dyeing, padding and printing fibers of animal origin,

e.g. wool, silk; synthetic polyamide fibers, e.g. nylon;

cellulosic fibers, e.g. cotton, linen; fibers of regenerated cellulose, e.g. viscose staple fiber, viscose and cuprammonium rayon; and mixtures and other articles of these fibers. The optimum conditions of application vary with the nature of the fiber and the dyes used. Animal fibers and synthetic polyamide fibers are dyed, printed or fixed preferably in acid, neutral or weakly alkaline medium, e.g. in the presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. Dyeing can also be carried out-in the presence of levelling agents, e.g. polyoxyethylated fatty amines or mixtures ofthe same and alkylpolyglycol ethers, in an acetic acid to neutral bath which is adjusted to-a neutral or weakly alkaline reaction at the end of dyeing'by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium carbonate or bicarbonate, or of compounds which react alkaline on heating, e.g. hexa-' methylene-tetramine or urea. The goods arethoroughlyrinsed and if necessary acidified with some acetic acid. 7

The dyeings obtained possess good fastness to light and wet agencies, e.g. washing, perspiration, milling, water, sea water and pot-ting, and good fastness to rub.- bing and dry cleaning (organic solvents).

trimethylamine, triethylene-diamine, or of asymmetrical dimet-hyl-hydrazine, or N-amino-pyrrolidine, preferably in stoichiometric amounts, accelerates the fixation of the dye on thefiber so that the fixing temperature can be lowered and/orthe fixation time reduced.

j The dyeings and prints. on'cellulosic fibers are notable for good light fastness, outstanding wet fastness'properties (washing, perspiration, water, sea water and alkali) and good rubbing and dry cleaning fastness. These prop erties are due to the formation of a stable chemical linkage between the dye molecule and the cellulose molecule. Often the total'amo'unt of dye applied does not take part inthe chemical reaction with the'fiber. In such cases the' portion of unreacted dye isremoved from the fiber by a suitable operation such as rinsing and/ or soaping, if nec-' essary at high temperatures. For this purpose synthetic detergents can be used, e.g. alkylarylsulfonates such as sodium dodecylbenzenesulfonate, alkyl sulfates such as sodium lauryl sulfate, alkylpolyglycolethers and mono-- or di-alkylphenyl-polyglycol ethers which maybe carboxymethylated or sulfated such as sodium lauryl polyglycol ether sulfate. I w

V In the following examples the parts and percentages arev by weight and the temperatures in degrees centigrade.

Example 1 V 57.6 parts of copper iphthalocyanine.are entered into 270 parts of chlorosulfonic acid. The solution is heated,

to 140 and held at this temperature for 1 hour. The temperature is then allowed to drop to 75 and parts of thionyl chloride are slowly added. The mass is stirred for 3 hours at 70-7 5and then discharged onto ice. The precipitated sulfonic acid chloride is filtered off, washed with dilute hydrochloric acid, and stirred into a mixture of 300 parts of ice and 700 parts of Water. 29

parts of 2-(3'-aminophenylamino)-4,5,6-trichloropyrimidine or 4-(3'-aminophenylamino)--2,5,6-trichloropyrimidine or a mixture of both compounds are added, The pH value is adjusted to v7 with dilute sodium hydroxide solution. Over the next 3 hours the ,pH value is maintained at7-8 by the gradual addition of dilute sodium hydroxide solution and the temperature is allowed to in crease from. 0 to 20. 35.7 parts of 4-arnino-l,l'-azobenzene-2',5r-disulfonic acid and 50 parts of sodium carbonate are addedand the reaction mass stirred for 48 hours at room temperature. The dye is precipitatedby the addition of hydrochloric acid and filtered ofli The filter cake is pasted with Water and neutralized with sodium hydroxide solution. The neutral paste is dried at 70- in vacuum. l v

A mercerized cotton fabric is printed with a paste of the following composition:

50 parts of the dye obtained-as described above, parts of urea, 365 parts of Water, 450 parts ofa 3% sodium alginate thickening,

10 parts of sodium 3-nitrobenzene-l-sulfonate, and 25 parts of sodium carbonate 7 1000 parts total 7 The fixation of the dyes on cellulosic fibers is normally efiected by heating. A number of dyed or fixed at lower temperatures, 'e .g.

. The-print is dried, steamed for 10 minutes at 102-l04,-

7 Example 2 89.6 parts of copper phthalocyanine-4,4',4",4"-tetrasulfonic acid are entered into 270 parts of chlorosulfonic acid and heated forl hour at 120. The temperature is allowed to drop to 70-75 and 90 parts of thionyl chlo ride are slowly added. The mass is stirred for 3 hours at 70-75" and then run onto ice. The precipitated sulfonic acid chloride is filtered off, washed with dilute hydrochloric acid and stirred into a mixture of 300 parts of ice and 700 parts or" water. 18.8 parts of 1,4-diaminobenzene-2-sulfonic acid and 35.7 parts of 4-amino-1,1-azobenzene-2,5'-disulfonic acid are added and the mixture neutralized with sodium hydroxide solution. 80 parts of sodium bicarbonate are added and the mass stirred for 48 hours at a temperature increasing from to 20. The dye is precipitated by the addition of hydrochloric acid, filtered off and Washed with dilute hydrochloric acid. The filtercake is stirred into 1000 parts of water, the pH value adjusted to 7 with sodium hydroxide solution, and the solution heated to 7085. 21.2 parts of 2,4-dichloro-5- chloromethyl--methylpyrimidine are added and the pH value maintained at 7-8 by the gradual addition of dilute sodium hydroxide solution. As soon as no more alkali is consumed the condensation reaction is completed. The dye is precipitated with common salt, filtered oif and dried at 80 in vacuum.

This dye is applied by the following procedure:

3 parts of the dye are dissolved in 100 parts of water, A

and to the solution are added 10 parts of urea, 30 parts of a 10% sodium carbonate solution and 0.5 part of sodium 3-nitrobenzene-l-sulfonate. A viscose filament fabric is impregnated with this solution, squeezed to retain 75% of its weight of the solution, dried, steamed with wet steam 5-10 minutes at 102, rinsed, soaped at the boil for 15 minutes, and dried. A green dyeing of very good Washing and light fastness is obtained.

Example 3 A suspension of sulfochlorinated copper phthalocyanine f is prepared as described in Example 1. 15 parts of 1- amino-3-acetylaminobenzene are added and the suspension is neutralized. with dilute sodium hydroxide solution.

During the next 3 hours the pH value is held at 7 by the v I tered off and washed well with dilute hydrochloric acid.

The filter cake is stirred into 600 parts of Water, the solution neutralized with sodium hydroxide solution and cooled to 0-5.

addition of a solution of sodium carbonate. As soon as no more alkali is consumed the condensation is com- 18.4 parts of cyanuric chloride are added. The pH value is maintained at 4-5 by the gradual pleted. The dye is precipitated with common salt, filtered To a suspension of sulfochlorinated copper phthaloat fwashed with dilute hydrochloric acid. The filter cake is of dilute sodium hydroxide solution.

cyanine prepared as given in Example 1' are'added 29 parts of a condensation product of 1 mole of 1,3-diaminobenzene and 1 mole of 2,4,5,6-tetrachloropyrirnidine and 44.5 parts of the compound:

The mixture is neutralized with dilute sodium hydroxide solution. By the gradual addition of sodium hydroxide solution the pH value of the mixture is maintained at 6-7 for the next 5 hours at room temperature and for the following 5 hours at60-65 It is then cooled to room temperature. Sodium hydroxide solution is slowly added until a clear solution is formed. This isstir red for 30 minutes, then neutralized with hydrochloric acid, and the dye precipitated with common salt. The precipitate is filtered oit, washed with salt solution, and the filter cake dried at 80 in vacuum.

Example 5 The moist filter cake of the tetrasulfonic acid chloride obtained from 57.6 parts of copper phthalocyanine according to Example 1 is stirred into a mixture of 300 parts well with dilute hydrochloric acid. The filter cake is stirred into a mixture of 800 parts of water and 50 parts of 30% hydrochloric acid at 0. An aqueous solution of 6.9 parts of sodium nitrite is added'dropwise. The suspension is stirred for 1 hour at 0 and then run slowly into a solution of 32.3 parts of 1-(2,5-dichlorophenyl)-3- methyl-S-pyrazolone-4'-sulfonic acid in 300 parts of water,- 1 '200parts of ice and parts of 30% sodium hydroxide "solution.

The green solution is stirred overnight. To saponify the acetylamino group 300 parts of 30% hydrochloric acid are added and the mass heated for 3 hours The precipitated intermediate is filtered off and dissolved neutral with 600- parts of water and sodium hydroxide solution. The solution is heated to 80, 22 parts of 2,4,5,6-tetrachloropyrimidine-are added, and the pH value maintained between 5 and 7 by'the gradual addition .As soon as no further sodium hydroxide solution is consumed, the con densation is finished. The dye is precipitated with sodium chloride, filtered off and dried at 80 in vacuum. Similar dyes are obtained when in place of 22 parts of 2,4,5,6- tetrachloropyrimidine, 18.5 parts of 2,4,6-trich1oropyrimidine or 21.5 parts of 2,4-dichloro-5-chloromethyl- 6-methylpyrimidine are used at the same temperature of condensation.

Example 6 The moist paste of copper-phthalocyanine -3,3",3",3"'- tetrasulfonic acid chloride obtained from 57.6 parts of copper-phthalocyanine according to the details of Example 1 is stirred in 300 parts of ice and 700 parts of water, 18.8 parts of 1,3-diaminobenzene 4-sulfonic acid and 35.7 parts of 4-amino-1',1'-azobenzene-2,5'-disulfonic acid are added and the mixture neutralized with 30% sodium hydroxide solution. After the addition of 7 parts of 25% ammonia (0.1 mole of NH and 60 parts of sodium bicarbonate the mixture is stirred for 30 hours at room temperature and then heated to 60. The dye is precipitated by the addition of sodium chloride, filtered off and washed with a solution of sodium chloride. The dye paste is dissolved in 1200 parts of Water at 50 and 21.2 parts of 2,4- dichloro-5 chlorornethyl-6-methylpyrimidine are added. The mixture is heated to 80 and stirred at 8090 until no free amino group more can be detected. During this time the pH value is held at 6-7 by the addition of a sodium carbonate solution. When the reaction is complete, the dye is precipitated by the addition of sodium chloride, filtered oil at about washed with a sodium chloride solution, dried and ground. A green powder is obtained which dissolves in water with a green coloration and dyes cellulosic fibers according to the dyeing process described in Example 2 in green shades fast to light, Wash ing, water, perspiration and rubbing.

Example 7 A solution prepared mutatis mutandis according to the particulars of Example 3 so that it contains parts of the dye of the formula carbonate solution. When free amino group can no longer be detected the reaction is completed. The dye is precipitated with sodium chloride, filtered off and dried at 40 or 3 parts of hexamethylene tetramine are added, and the bath is maintained at for 20 minutes. The fabric is removed from the bath, then rinsed thoroughly, acetic acid being added to one of the rinsings, and subsequently dried. A level green dyeing of good fastness to light,

washing, milling, perspiration, rubbing and dry cleaning is obtained.

The following table gives details of further phthalocyanine dyes of Formula I which are produced according to the procedure described in the specification, especially in Examples 1 to 7. In the table they are characterized bythe phth alocyanine-from which PC is derived and the positions of the substituents (column I), the aminoazo dye fromvwhich RI N it is derived (column II), the radical R (column III), the reactive component from which Z is derived (column IV), the symbols A A W, m, n, p and-q (columns V to XI), and the shade of the dyeing on cotton or wool (column XII).

113x. I II III V V VI VII VIII IX X XI XII 8 Copperphthnll-pbenyl-3- 1,4-phenylene 2,4,6-trichloro- H H 3 1 1 1 G e 0cyaninemethyl-4- pyrimidine. 3,3,3",3". (4"-aminophenylazo)- 5-pyrazolone- 2,5'-disulionic acid. 1 9 do do -d 2,-1.5,6-tetra- H CH; 3 1 1 1 Do.

chloropyrimidine. -CH2-CH2- do H H 3 1 1 1 D 4-amin0-1,1'- -CHr-CH2- B-Ohlor0pi0- 0H; H 3 1 1 1 D azobenzenenylchlorlde. 4'-sultonic acid. 12 d0 do 1,3-pheny1ene-. 2,4,6-trichlor0- H H 3 1 1 1 Do, 5-methylpyrimidine.

13 do 4-amino-I,1- d0 .2-(3'-sull0phe- H R 2 1 1 2 Yellowl h azobenzenenylamin0)- green, 2'-sulf0nic 4,6-dichloroacid. 1,3,5-triazine.

14..." Copperphthaldo do do H 3 l 1 1 Green.

ocyanme- 4,4,4",4". 1

15 do 1-phenyl-3- QFmethyI- H H 3 1 1 1 Do,

' methyl-'1- amino-4,6-

(4"amin0- dichlorophenylazo)- 1,3,5-triazine. 5-pyrazolone- S 01H 4'-sulf0nic acid.

16 Copperdo 2,4 ,fi,fi-tetra- H H 3 1 1 1 Do.

phthaloeychloropyenine 3,3, rimldtue. 3!!)3!!!- 7- -------.d0 -p y -----d 01H; H 3 1 1 1 Do.

methylA- phenylazo)- 5-pyrazolone- S 0 H 3',6-disulionic acid.

18 do do -0Hz-CHrOHr.-- Chlllciroagetyl H H"; NH; 2 2 1 1 Do.-

19 Copper- 4-amino-1,1- 2,4,64110111010- H H 3 1 1 1 D0.

phthalocyazobenzenepyrimidine. anine 4,4, 2',4-disul 4",4". tonic acid. A

20 Copperdo 2-(4-sullophe- H H 3 1 1 1 Do,-

phthalocynylaminO)- anine 3,3, 4,6-dichloro- 13):. I II III IV V VI VII VIII IX X XI XII 21 Copper- 4amin0-1,1- CH2CH B-Chloropro- H H 3 1 1 1 Do.

phthalocyazobenzeue- I pionylchloanie 3,3, 2,4-disul- CH; ride. 7 3",3. fonic acid.

22 do do 1,3 pheny1ene 2-(2-su1fo- CH; H 3 1 1 1 Do. ethy]amino)- 4,6-dich1oro- 1,3,5-triazine.

23 do 4-amino-4- rx-ChlOlO- H H 3 1 1 1 Do,

y ficrylylchloazobenzeneride. 2-su1i'onic acid. CH

24 do do CHz-CH 2-di-(fl-hy- H H NH; 1 3 1 1 Do.

I droxy-ethyb- CH3 amino-4,6-

dichloro- 1,3,5-triaz1ne.

25 do do 1,4-pheny1ene 2-amino-4,6- H H 3 1 1 1 Do.

dibromo- 1,3,5-triazinc.

26 do do (1o 2,4,6-trichloro- H H 2 1 1 2 Yellowish ropyrimigreen.

. dine.

27 do d0 2,4,5,6-tetra- H H 2 1 2 1 Green.

chioropyrimidinc.

SO H

28 do -amino-1,1- -do H H- 2 1 1 1 Do.

azobenzene- 2,5-disulionic acid.

29 do do CHz-CH2 Ohloroacetyl- H H 2 1 1 1 Do.

chloride.

30 do do 1,3-pheny1ene 2-(2,5-disulf0- H H 2 1 1 1 Do.

phenylamino)-4,6- dichloro- 1,3,5-triazine.

31 do do OaH 2,4,5,6-tetm- H H 3 .1 1 1 Do.

I bromopyrim- 32 do do .1 S0311 B-Bromopropi- H H 3 1 1 1 Do. l onlychloride.

33 do 4-amino-4- SO I-I 2-N-methy1-N CH H 3 1 1 1 D methoxy-1,1- I 2-su1foethy1- azobenzene-2- amino-4,6-disulfonic acid. ch10ro-1,3,5-

triazine.

34 d0 .110 03E 2,4,6-trich10ro H H NH1 2 2 1 1 Do.

| pyrimidine.

35 do l-phenyl-S- COOH- do H H 3 1 1 1 D0.

methy1-4-(3- I aminophenylazoyfi pyrazo1onc-4- sulfonic acid. 36 do d0 2,4,6-trich1oro- H II 3 1 1 1 Do.

5-carboxymethylpyrimidine. CI

37 d0 1( -methy1- 2,4,5,6-tetra- H H 3 1 1 1 Do.

pheny1)-3- chloromethyl-4-(4- pyrimidine. aminophenylazo)-5-py- C 2 razolone-, 6-disu1f0nic acid. 38 do 1 (2-methy1- 1,3-pheny1enc a-Chloro- H H 3 1 1 1 Do.

phenyl)-3- acrylylmethyH- chloride. (4-amin0- phenylazoy 5-pyrazolone-4 ,6 disulfonic acid. 39 copperphtha- 4-amin0-1,1- 2-(2',4-di- H H 3 1 1 1 Do,

l0cyanine-' azobenzencsuiiophenyi- 4,454 2',5'-disu1- ammo)-4,6-

ionic acid dichloro- S 0 H 1 ,8 ,5-triaozmc- 11%;. I II III IV VI VII VIII IX XI XII 40. copperphtha- 4-an1in0-1;1- fi-Chloropro- H 3 1 1 locyanineazobe-nzenepionylchlo- 4,4,4. 2,5-disu1- ride.

fonic acid.

41..." copperphthaimet-hyl- Z-(fi-l1ydroxy- H 3 1 1 D0 locyanineamino-4- ethylamino- 3,a',3",3'". methy1-1,1- 4,6-dibromoazobenzene- 1,3,5-triazinc. 2-sulionic S 03H acid.

42 do do chloroaeet'yl H CHg-NH 2 2 1 D v chloride.

43 do 4-amino-4'- -CH2 CH2- 2,4,6-trich1oro- H 3 1 1 Do.

methoxy- CHg-CHT fi-carboxy- 1,1-azobenpyrimidine.

zene-2-su1- ionic acid. 44..-" do "do. 1,3-pheny1ene Z-ethylamino- CH3 3 1 1 Do. 4,6-dich1oro- 1,3,5-triazine. 45--. Copperphthal- 4-amino-4- ---.dO 2,4-dichloro H 3 1 1 D0.

ocyaninech1oro-1,1'- 5-ch1or0- 3,3,3,3. azobenzenemethyl-6- 2'-su1ionic methyl-pyacid. rimidiue. 46 do 4-amino-2- ..do 2-carboxy- H 3 1 1 Do.

methyl-1,1- methylazobenzeneamino-4,6- 2,5'-disu1- dichloroionic acid. 1,3,5-triazine. 47 do do -OHz-CHz- 2,4,6-tribmmo- H 3 1 1 Do,

fi-methylpyrimidine. 48 do 4-amino-3- 1,3-pheny1ene 2,4,6-trichlor0- H HO-C H 2 2 1 Do.

- methy1-1,1- 5-bromopy- H- azobenzenerimidine. 2',5'-disu1- ionic acid. 49m" Gopperpiitha- Lamina-2,5- d0 Cyanuric ch1c- H 3 1 1 Do.

locyanmedimcthyl ride.

4,4',4,4. 1,1-azobenzene-2,5'-disultonic acid. 50 do o d0 2,4,6tribromo- H 1 1 D pyrimidine. 51 do 4-amino-2- 2,4,6-trichloro H 3 1 .1 Do.

methy1-5- fi-chlorm methoxymethyl- 1,1-azobenpyrimidine. zene-2',5"- 0 H disulfonic acid. 52 do do 2,4,6-trichl0ro- H 3 1 1 Do.

5-carb0- metjaogrgi'l-l pyrum e. OCHa 53.--" Copperdo COOH 2,4,15,6-tetra- H 3 1 1 Do.

phthaio- I, chioropyrimcyamneidine. /5 /11 54...... do 4-amino-2- COOH 2,4,6-trich1oro- H 3 1 1 D0.

methyl-E- I 5-brornomethoxy1,1- pyrimidine. azobenzene- 4-sulfonic acid. 55 d0 do SOaH 2,4-dichIoro-5- H 3 1 1 Do.

chloromethylpyrimidine.

56 dodo- GH:OH; 2,4-d1ch1cr0-6- H 3 1 1 Do.

(2's11li0- ethy1amin0)- 1,3,5-triazine. 57 do i-amino- 1,8-pheny1ene Bromoacetyl acetylchloride. amino-1,1- azcbenzene- 4-sulonic acid.

58 do do do 2,4,6-tr1br0m0- H 3 1 1 Do.

5-carboxymethyl pyrimidine.

59 Copper- 4-amino-2-su1- 803B 2,4-dibromo-5- H 2 1 1 Do.

phthalofoacetyil bromw cyanineamino-1,1- methyl-6- 3,3,3". azobenzenemethylpy- 3'-is11fonic rimidine. ac

23 24 the four substituents being in the positions 3, 3', 3" and and 3III. Example HO\ [Last paragraph] C-N- 80 11 1 V 5 N N=NG l ---SO|HZ Cl -0 oo=N H- I ll a l N\ /CH CH3 z- \C -0 i R is a member selected from the group consisting of J 1,3-phenylene, 4-sulfo-1,3-phenylene and'3-sulfo-L4- CuPO C1 phenyle'ne, and 110 Z is a member selected from the group consisting of v so H chloracetyl, 4,6-dichloro-1,3,5-triaziny1-2, 4-amino-6- a chloro-1,3,5-triaziny1-2, 2,4-dichloro-6-methyl-pyrimi- 0 i I dyl-S-methylene,

so H (|J=N I 3 OH: O -o1 the four substituents being in the positions 3, 3', 3" v g and 3". V -o 0-01 Example 6 N 1 N and or n -so E I oH3o o o1 0 0l -SO;,NH2 NH-OHz-O N l l f 1 g i-ol SO:NH- -SOaH I -o C-CI CuPO 01 \N/ s0 g 2. The dyestuif of the formula S0a-NHON=N N J s0lrn1 ei SOzH V NH- n the four substituents being in the positions 3, 3, 3" 5 /C C1 and 3'" r S02--NH 0 Example 7 OuPO ('31 oom),

NHCOCH;C1 40 CuPC --SO NH SOBH J S OaH T O 4 21:1 fgur substltuents being 1n the positlons 3, 3 3

3. The d estuff of the formula the four substituents being in the posltions 3, 3, 3" y and souz SOaH Having thus disclosed the invention what I claim 1s: l g1 1. Dyestuif of the formula C Q\ )H w a )2 CuPO TS0aNHRzNH-Z (MP0 01 SO H J SOz-NH R1 I 3 wherein --sOz-NH R is a member selected from the group consisting of l J the radicals S OH 8011 the four substituents being in the positions 4, 4', 4"

3 1n 7 I and 4 r C 4. The dyestufl of the formula 01 SOBH 0aH)a (Il the four substituents being in the positions 3, 3', CH3 n 3!"I 25 5. The dyestuff of the formula OuPC so NH so a the four substituents being in the positions 3, 3', 3"

and 3".

6. The dyestufl of the formula CuPC the four substituents being in the positions 3, 3', 3

the four substituents being in the positions 3, 3', 3"

and 3".

OuPO

C=N SO3H I 15 the four substituents being in the positions 3, 3', 3" and 3'.

9. The dyestutf of the formula the four substituents being in the positions 3, 3, 3" and 3.

10. The dyestuff of the formula N H-C 0-CH2-C1 the four substituents being in the positions 3, 3', 3 and 3'.

References Cited in the file of this patent UNITED STATES PATENTS 3,082,201 Koller Mar. 19, 1963 FOREIGN PATENTS 50 1,221,621 France Ian. 18, 1960 UNITED STATES PATENT OFFICE CERTIFICATE. OF CORRECTION Patent No. 3,133,050 May l2, 19 4 Hans von Tohel It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 34 for "-ethylamine read ethy'laminbcolumns 11 and 12, in the table, under the heading "III", and opposite Ex. No. 17, the formula should appear as shown below instead of as in the patent:

' SO H same table, under the heading "IV", and opposite Ex, N0. 11, for "Bchloropionylchloride"' read Bchloropropio'nyl-chloride columns 13 and 14, in the table, under the heading "I", and opposite Ex. No, 21, for "phthalocyanie" read. pht-halocyanine same table, under the heading "IV", and opposite Ex. N0. 32, for "B-Bromopropionly" read @3-Bromopropionyl same table, under the heading "IV", and opposite Ex. No. 39, for "-triaozine-" read 'triazinecolumns 17 and 18, in the table, under the heading "II", and opposite Ex. No; 60, for "azobenzine-3 sulfonic acid read azobenzene,3- sulfonic acid columns 21 and 22, in the table, under the heading "IV", and opposite EX No. 104, for "1,3,3-triazine" read 1,3,5-triazine column 23, the first formula under "Example 5", for the upper left-=handportion of the formula reading "SO H read -(SO l-D 2 Signed and sealed this 22nd day of December 1964.

(SEAL) Attest:

ERNEST W. SWI'DER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. DYESTUFF OF THE FORMULA 